JP2009013473A - Thin-film-forming apparatus and thin-film-forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin-film-forming apparatus which can form a thin film of high quality uniformly and stably on both sides of a film. <P>SOLUTION: Film-forming chambers 5a and 5b are connected to a transfer chamber 3 and are decompressed by vacuum pumps 9a to 9c respectively. A transportation system for the film 15 ranging from an unwinding drum 13 to a winding drum 31 is formed in the transfer chamber 3. Heating means 17a to 17f for heating the film 15, the first film-forming means 25a for forming the thin film on one side of the film 15, and the second film-forming means 25b for forming the thin film on the other side of the film 15 are installed in between the unwinding drum 13 and the winding drum 31. The film 15 is put under decompression conditions and not exposed to the air, while the film 15 is unwound from the unwinding drum 13, has the thin film formed on both sides thereof and is wound up by the winding drum 31. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thin film forming apparatus and a thin film forming method for forming an inorganic or organic thin film on a film.

The thin film forming apparatus is an apparatus that continuously forms a thin film on a roll-shaped film. A film on which a gas barrier thin film is formed (hereinafter referred to as a gas barrier film), a magnetic recording tape, an antireflection film, and the like can be produced in large quantities.

  Gas barrier films are used for packaging substrates for electronics elements such as liquid crystal display elements, electroluminescence display elements, touch panel elements, etc., in addition to packaging applications for foods, drinks, pharmaceuticals, chemicals, daily necessities, miscellaneous goods, and various items. A gas barrier film having a uniform and high quality is required. In particular, a flexible display substrate using a transparent resin film as a substrate is expected in accordance with the trend that liquid crystal displays are required to be small, light, thin, and strong. In addition, organic electroluminescence displays have attracted widespread attention as electroluminescence display elements, and can contribute to extending the life of light emitters by enhancing the gas barrier properties of gas barrier films.

  When the gas barrier film is produced, if the heating is performed prior to forming the gas barrier thin film on the resin film, the gas barrier property is improved as compared with the case where the heating is not performed. (For example, see Patent Document 1 Table 1 and Table 2) However, when forming a gas barrier thin film on both sides with an apparatus having only one system for forming a thin film, the resin film is heated to form a gas barrier thin film on one side. After that, it is necessary to break the vacuum of the apparatus, reverse the front and back of the resin film, and form a gas barrier thin film on the other surface. In this case, since the effect of the first heating is lost, it is necessary to heat again before the second thin film formation.

  Further, the following apparatuses are known as apparatuses used for producing a gas barrier film. That is, the entire apparatus is accommodated in a vacuum chamber, and the vacuum chamber is divided into two areas, a conveyance region and a thin film formation region. The conveyance area has a conveyance system such as unwinding and winding of the original fabric and a cooling drum, and the thin film formation area has a plurality of thin film formation systems. A part of the drum surface of the cooling drum is exposed from the transport area to the thin film forming area. If one cooling drum and a plurality of thin film forming systems are provided, it is possible to form a plurality of types of thin films on one side of the film, but it is impossible to form a thin film on both sides of the film. Moreover, heating the resin film before forming a thin film is not performed. (For example, see Patent Document 2 FIGS. 4 and 6)

Also, as a device for forming a gas barrier thin film on both sides of a resin film, two sets of a cooling drum and a thin film forming device are used, and the device is configured so that the film is reversed between the two sets. ing. If there are two cooling drums and two thin film forming systems, it is possible to form a gas barrier thin film on each of both surfaces of the film by devising the film path. However, heating the film before forming the thin film is not performed. (For example, see Patent Document 3 FIG. 2)
JP 2005-169994 A JP 2005-169267 A JP 2000-338901 A

  The conventional thin film forming apparatus has a problem that the composition of the formed gas barrier thin film is not constant, and the gas barrier property after the thin film is formed changes during storage.

  This is because the roll-shaped film contains moisture depending on the season and the material, and even if evacuation is performed, the film is still in the roll shape. This is to influence. In recent years, metal oxide films have been widely used as transparent deposits, and silicon oxides such as silicon oxide, silicon nitride, and silicon nitride have attracted attention as gas barrier thin films because of their high barrier properties. . However, since these silicon compounds have different colors and gas barrier properties depending on the composition ratio of oxygen, when a thin film is formed with a conventional apparatus having an unstable atmosphere, thin films with different colors and gas barrier properties are formed as they progress. . In addition, when a gas barrier thin film is formed only on one side of the film, the gas barrier thin film reacts with oxygen contained in the film during storage and changes in quality.

  The present invention has been made in view of such problems, and its object is to form a thin film having a uniform and high-quality composition on the film.

In order to achieve the above-mentioned object, the first invention is a first means for forming a thin film on one side of the film, a conveying means for unwinding and conveying the roll-shaped film, a heating means for heating the film. A thin film forming apparatus comprising: a film forming unit; a second film forming unit that forms a thin film on the other surface of the film; and a winding unit that winds the film.
The transfer means, the heating means, and the winding means are provided in a transfer chamber, and the first film formation means and the second film formation means are provided in a film formation chamber. The film formation chamber has a vacuum exhaust means. The evacuation means is, for example, a cryopump. It is desirable to provide pretreatment means for performing pretreatment on the surface of the film before forming a thin film.
The heating means is an infrared heating device, a microwave heating device, a heating drum, or the like. The film forming means is a vacuum deposition film forming apparatus, a sputtering film forming apparatus, an ion plating film forming apparatus, an ion beam assisted film forming apparatus, a cluster ion beam film forming apparatus, a plasma CVD film forming apparatus, a plasma polymerization film forming apparatus, a heat A CVD film forming apparatus, a catalytic reaction type CVD film forming apparatus, or the like. The film forming means has a plurality of film forming apparatuses and can form a multilayer film of the same or a plurality of materials. The thin film formed on the film is an inorganic silicon compound. In the silicon compound, it is desirable that the value of the atomic quantity ratio of the oxygen component of the thin film is within 4.5% at the start of film formation and at the end of film formation.

2nd invention forms a thin film on the single side | surface of the said film, the evacuation process which decompresses a vacuum chamber, the conveyance process which unwinds a roll-shaped film in the said vacuum chamber, the heating process which heats the said film A thin film forming method comprising: a first film forming process; a second film forming process for forming a thin film on the other surface of the film; and a winding process for winding the film.
Moreover, before forming a thin film in the said film, it is desirable to provide the pre-processing process which pre-processes on the surface of the said film.

  In the present invention, the atmosphere in the film formation chamber is not affected by the moisture contained in the film by heating the film, removing the moisture contained in the film, and then forming a thin film without touching the air. The thin film to be formed is uniform and of high quality. In addition, since the thin film is formed on the other surface without being exposed to the air after the thin film is formed on one surface, the thin film can be formed on both surfaces of the film with little moisture contained in the film. Therefore, even if the film after forming the thin film is stored in the air, the film does not absorb moisture, and the thin film does not change in quality and has high stability.

Hereinafter, a thin film forming apparatus and a thin film forming method according to an embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a diagram showing a thin film forming apparatus 1 according to an embodiment of the present invention.

The thin film forming apparatus 1 includes a transfer chamber 3 and film formation chambers 5a and 5b. The transfer chamber 3 includes a vacuum pump 9c via a valve 7c, and the film formation chamber 5a includes a vacuum pump 9a via a valve 7a. The film forming chamber 5b is provided with a vacuum pump 9b through a valve 7b. As the vacuum pumps 9a to 9c as the vacuum exhaust means, a dry pump, a turbo molecular pump, or a cryopump is used, and the pressure can be reduced to 9.0 × 10 ⁻⁵ Pa.

  In the transfer chamber 3, an unwind drum 13 and guide rollers 19a to 19p are provided as transfer means. A roll-shaped film original 11 of the film 15 is attached to the unwinding drum 13 so that the film 15 can be unwound freely.

  Examples of the material of the film 15 include polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polycarbonate film, polyamide, polyimide, polyamideimide, polyarylate film, polyethersulfone film, polysulfone film, polyarylate, and a ring containing norbornene. Examples include olefin polymers, acrylic resins, epoxy resins, and combinations thereof.

  The thickness of the film 15 is preferably 12 to 200 μm, more preferably 100 μm. When the thickness of the film 15 is within the above range, the film 15 is easy to bend and is not broken during conveyance, and is easy to handle with the thin film forming apparatus according to the present invention.

  The moving speed of the film 15 is not particularly limited, but is preferably 0.01 m / min to 10 m / min, more preferably 0.1 m / min.

  The transfer chamber 3 is provided with heating means 17a to 17f for removing moisture from the film 15 unwound by the unwinding drum 13, and guide rollers 19a to 19e for moving the film 15 in the heating means. ing. In FIG. 1, both surfaces of the film 15 are heated three times each by six heating means. However, the number of the heating means 17 a to 17 f may be reduced or increased depending on the type of the film 15.

  The type of the heating means 17a to 17f is not particularly limited as long as the film can be heated to about 100 ° C. under reduced pressure, but is preferably an infrared heating device, a microwave heating device, or a heating drum.

  The infrared heating device is a device that heats the film by emitting infrared rays from the infrared ray generating means. Moreover, a microwave heating apparatus is an apparatus heated by irradiating a film with a microwave from a microwave generation means. The heating drum is a device that heats the film by increasing the temperature of the drum surface and conducting heat from the contact portion of the wound film.

  The transfer chamber 3 is provided with guide rollers 19f to 19g for guiding the heated film 15 to the film formation chamber 5a. Pre-processing means 21a for pre-processing the film 15 is provided in front of the guide roller 19g.

    The pretreatment means 21a is a corona treatment device, a low temperature plasma treatment device, a glow discharge treatment device, or the like. By taking these measures, the shape and chemical properties of the resin surface of the film can be changed, and the adhesion between the film and the thin film formed on the film can be improved.

  In the film forming chamber 5a, a coating drum 23a for winding the pre-processed film 15 is provided. A part of the coating drum 23a is exposed to the transfer chamber 3, and the film 15 moves from the transfer chamber 3 to the film forming chamber 5a while being wound around the coating drum 23a.

  The film forming chambers 5a and 5b are provided in contact with the transfer chamber 3, and can move without the film 15 being exposed to the atmosphere. The film forming chamber 5a and the transfer chamber 3 are connected by a rectangular hole, and a part of the coating drum 23a protrudes toward the transfer chamber 3 through the rectangular hole. A gap is opened between the coating drums 23a, and the film 15 can move from the transfer chamber 3 to the film forming chamber 5a through the gap. The structure between the transfer chamber 3 and the film forming chamber 5b is similar, and the film 15 can be moved without being exposed to the atmosphere.

The purpose of the coating drum 23a is to prevent the film 15 from absorbing water again after being heated by the heating means 17, and to prevent shrinkage or breakage of the film 15 due to heat when forming a thin film by the film forming means 25a.
The coating drum 23a may be made of stainless steel and may have a temperature adjusting means from −20 ° C. to 50 ° C.

  The film forming chamber 5a is provided with a film forming means 25a so as to cover a part of the coating drum 23a. A thin film is formed on one side of the film 15.

  The film forming means 25a is provided with a gas supply port 27a through a valve 29a, and various gases are supplied to the gas supply port 27a depending on the substance forming the thin film, if necessary.

  As the film forming means 25a, a vacuum film forming apparatus, a sputtering apparatus, an ion plating film forming apparatus, an ion beam assisted film forming apparatus, a cluster ion beam film forming apparatus, a plasma CVD film forming apparatus, a plasma polymerization film forming apparatus, and a thermal CVD. There are a film forming apparatus, a catalytic reaction type CVD film forming apparatus, and the like.

  The film forming means 25a may be provided with one film forming apparatus or two or more of the same or different kinds of film forming apparatuses.

  The thickness of the thin film formed by one film forming apparatus is preferably 20 nm to 200 nm, and more preferably 100 nm.

  When a thin film is formed thickly by one film forming apparatus, the thin film becomes brittle due to stress, cracks are generated, the gas barrier property is remarkably lowered, and the thin film is peeled off during transportation or winding. Therefore, in order to obtain a thick layer of a gas barrier thin film, it is preferable to provide a plurality of film forming apparatuses and form a thin film of the same substance a plurality of times.

  In addition, thin films of different materials may be formed by a plurality of film forming apparatuses. In that case, a multilayer film having various functions as well as gas barrier properties can be obtained.

  The material forming the thin film is not particularly limited, but when used as a gas barrier thin film, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, Examples thereof include metal oxides such as indium oxide, zinc oxide, and zirconium oxide, or metal nitrides, carbides, and mixtures thereof.

  Guide rollers 19h to 19m are provided in the transfer chamber 3 in order to guide the film 15 having a thin film formed on one side, which has been moved again to the transfer chamber 3 by the coating drum 23a, to the next film formation chamber 5b. The transfer chamber 3 is provided with pretreatment means 21b for pretreatment before the film 15 is wound around the coating drum 23b. The preprocessing unit 21b is the same as the preprocessing unit 21a.

  Similar to the film formation chamber 5a, the film formation chamber 5b is provided with a coating drum 23b and a film formation means 25b. Similarly to the film forming means 25a, the film forming means 25b is provided with a gas supply port 27b through a valve 29b. The film 15 having a thin film formed on one surface is formed on the other surface by the film forming means 25b, and finally the thin film is formed on both surfaces of the film 15. The coating drum 23b, film forming means 25b, gas supply port 27b, and valve 29b are the same as the coating drum 23a, film forming means 25a, gas supply port 27a, and valve 29a, respectively.

  Guide rollers 19 n to 19 p are provided in the transfer chamber 3 in order to guide the film 15 having thin films formed on both sides thereof, which has been moved again to the transfer chamber 3 by the coating drum 23 b, to the take-up drum 31. The transfer chamber 3 is provided with a take-up drum 31 as a take-up means for winding the film 15 on which a thin film is formed into a roll.

  Next, the operation of the thin film forming apparatus 1 will be described. The roll-shaped film original 11 is installed on the unwinding drum 13 in the transfer chamber 3, and the pressure in the transfer chamber 3 and the film forming chambers 5a and 5b is reduced by the vacuum pumps 17a to 17c.

  When the predetermined pressure is reached, the film 15 is unwound from the original film 11 by the unwinding drum 13. The film 15 is heated by the heating means 17a to 17f, and the moisture inside the film 15 is removed before forming the thin film.

  The heated film 15 is guided to the pretreatment means 21a to perform pretreatment. The pretreated film 15 is moved from the transfer chamber 3 to the film forming chamber 5a while being wound around the coating drum 23a. A thin film is formed on one surface of the film 15 wound around the coating drum 23a by the film forming means 25a.

  The film 15 having a thin film formed on one side is moved again to the transfer chamber 3 by the coating drum 23a. Thereafter, the inside of the transfer chamber 3 is moved by the guide rollers 19h to 19m, and pre-processing is performed by the pre-processing means 21b. The film is wound around the coating drum 23b so that the surface on which the thin film is not formed becomes the front side, and moves to the film forming chamber 5b. In the film forming chamber 5b, a thin film is formed on the other surface of the film 15 by the film forming means 25b.

  The film 15 with the thin film formed on both sides is moved again to the transfer chamber 3 by the coating drum 23 b, and the film 15 is wound up in a roll shape by the winding drum 31.

  Thus, according to the present embodiment, the film 15 is heated before the thin film is formed, and the water adsorbed by the film 15 is removed, so that the atmosphere in the film forming means 25a and 25b is improved, and A high-quality gas barrier film can be obtained.

  In particular, when the silicon nitride thin film is formed, the water adsorbed on the film 15 is removed, so that the oxygen concentration in the atmosphere of the film forming means 25a and 25b is reduced, and the oxygen nitride having a low oxygen composition is reduced. A silicon silicide thin film can be obtained.

  Moreover, since a thin film can be formed on both surfaces simultaneously without exposing the film 15 to the atmosphere, moisture absorption of the base film during storage, and denaturation and peeling of the formed thin film can be prevented, and a stable gas barrier film is obtained. be able to.

  Next, the results when the thin film is actually formed using the thin film forming apparatus 1 shown in FIG. 1 will be described.

  In the film forming means 25a and 25b shown in FIG. 1, a dual magnetron sputtering apparatus is disposed as a film forming apparatus. This sputtering apparatus was equipped with a silicon target. In addition, an infrared heating device was disposed as the heating means 17a to 17f.

  Next, a roll-shaped biaxially stretched polyethylene naphthalate film (PEN film Q65 manufactured by Teijin DuPont Co., Ltd., thickness: 100 μm) having a width of 30 cm is prepared as the original film 11, and the unwinding drum 13 is formed with the untreated surface side of the resin film as the outside. Attached to.

Next, the inside of the transfer chamber 3, the film forming chamber 5a, and the film forming chamber 5b is evacuated. After reducing the pressure to a level of 10 ⁻² Pa using a dry pump or a turbo molecular pump, the pressure was reduced to an ultimate vacuum of 9.0 × 10 ⁻⁵ Pa using a cryopump. Next, after raising the coating drums 23a and 23b to 50 ° C., the resin film 15 was conveyed at a speed of 0.1 m / min, and the degassing process was performed by setting the infrared heating devices 17a to 17f to 100 ° C. .

Nitrogen gas (manufactured by Taiyo Toyo Oxygen Co., Ltd. (purity 99.9999% or more)) and argon gas (manufactured by Taiyo Toyo Oxygen Co., Ltd. (purity 99.9999% or more)) are prepared as additive gases during film formation. The gas supply ports 27a and 27b can supply the film forming means 25a and 25b with nitrogen gas introduced into the film forming means 25a and 25b at a flow rate of 15 sccm and argon gas at a flow rate of 20 sccm. After setting the drums 23a and 23b to 0 ° C., the resin film was run, the power was turned on at 1.0 kW, and the thin film formation was started while maintaining the internal pressure of the film forming means 25a at 1.0 × 10 ⁻¹ Pa. The film forming means 25a and 25b are under the same conditions, and sccm means standard cubic centimeter per min. te stands for.

  A gas barrier thin film made of silicon nitride was formed on the resin film 15 to obtain a gas barrier film. Although oxygen is not included in the gas supplied to the film forming means 25a and 25b, oxygen is included in the film forming atmosphere due to water contained in the resin film 15, and the formed gas barrier thin film is a pure chip. It becomes silicon oxide silicon instead of silicon oxide. The running speed of the resin film 15 was set so that the thickness of the silicon nitride oxide film formed at the start of thin film formation was 100 nm. Such a silicon oxide thin film was continuously formed on a 400 m resin film.

  When the atomic ratio of oxygen components was measured by X-ray photoelectron spectroscopy for the silicon nitride oxide film, which was the starting site and the final site of the above thin film formation, the results were as shown in Table 1. The starting site was 8.1%, whereas the final site was 7.4%. Further, the atomic quantity ratio of the oxygen component on the back surface was 10.3% at the start site, whereas it was 8.8% at the final site. Thereby, it was confirmed that the oxygen component hardly changed and the stable thin film formation was maintained.

(Comparative example)
On the other hand, as a comparative example, a thin film was formed only on one side without subjecting the resin film to heat treatment, and a film having a thin film formed on one side was prepared in the same manner as in the examples.
When the atomic ratio of oxygen components was measured for the silicon nitride oxide film that was the start and end of the continuous film formation, the results were as shown in Table 2. The starting site was 18.2%, while the final site was 13.4%. It was confirmed that the oxygen composition changed with time.

  Comparing the examples and the comparative example, it can be seen that the gas barrier film of the example has a smaller amount of oxygen contained and less variation in the amount of oxygen, and a more preferable gas barrier film was obtained. .

  The preferred embodiments of the thin film forming apparatus and the thin film forming method according to the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to such examples. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea disclosed in the present application, and these are naturally within the technical scope of the present invention. Understood.

It is a figure which shows the thin film forming apparatus which concerns on the Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ......... Thin film-forming apparatus 3 ......... Conveying chamber 5 ......... Deposition chamber 7 ......... Valve 9 ......... Vacuum pump 11 ......... Original film 13 ...... Unwinding drum 15 ......... Film 17 ......... Heating means 19 ......... Guide roller 21 ......... Pretreatment means 23 ......... Coating drum 25 ...... Film forming means 27 ......... Gas supply port 29 ......... Valve 31 ......... Winding drum

Claims (12)

A conveying means for unwinding and conveying the roll film;
Heating means for heating the film;
First film forming means for forming a thin film on one side of the film;
A second film forming means for forming a thin film on the other surface of the film;
A winding means for winding the film having a thin film formed on both sides into a roll;
A thin film forming apparatus comprising:   2. The transfer means, the heating means, and the winding means are provided in a transfer chamber, and the first film formation means and the second film formation means are provided in a film formation chamber. Thin film forming equipment.   The thin film forming apparatus according to claim 1, wherein the film forming chamber has a vacuum exhaust unit.   4. The thin film forming apparatus according to claim 3, wherein the evacuating means is a cryopump.   4. The thin film forming apparatus according to claim 1, further comprising pretreatment means for performing pretreatment on the surface of the film before forming a thin film in the film forming chamber.   4. The thin film forming apparatus according to claim 1, wherein the heating means is one of an infrared heating device, a microwave heating device, and a heating drum.   The film forming means includes a vacuum deposition film forming apparatus, a sputtering film forming apparatus, an ion plating film forming apparatus, an ion beam assist film forming apparatus, a cluster ion beam film forming apparatus, a plasma CVD film forming apparatus, a plasma polymerization film forming apparatus, 4. The film forming apparatus according to claim 1, wherein the film forming apparatus is one of a thermal CVD film forming apparatus and a catalytic reaction type CVD film forming apparatus.   The thin film forming apparatus according to claim 1, wherein the film forming unit includes a plurality of film forming apparatuses and can form a multilayer film of the same or a plurality of materials.   4. The thin film forming apparatus according to claim 1, wherein the thin film formed on the film is an inorganic silicon compound.   10. The thin film forming apparatus according to claim 9, wherein, in the inorganic silicon compound, an atomic quantity ratio value of oxygen components of the thin film is within 4.5% at the start of film formation and at the end of film formation. An evacuation step of depressurizing the transfer chamber and the film formation chamber;
A conveying step of unwinding a roll film in the conveying chamber;
A heating step of heating the film;
A first film forming step of forming a thin film on one side of the film;
A second film forming step of forming a thin film on the other surface of the film;
A winding process for winding the film;
A thin film forming method comprising:   The thin film forming method according to claim 11, further comprising a pretreatment step of performing a pretreatment on the surface of the film before the first film formation step and the second film formation step.

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